Silicon oxide resins and process of making same



Patented Apr. 25, 1950 orricia SILICON OXIDE RESINS AND PRQCESS OFMAKING SAME John B. Rust, West Orange, and Homer van B. Joy, Montclair,N. J., a'ssignors, by direct and mesneassignments, of one-half toMontclair Corporation, a corporation of New Jersey, and one-hall toEllis-Foster Company, a corporation of New Jersey No Drawing.Application June 20, 1944,

' Serial No. 541,294

Claims.. (Cl. 260-465) The present invention relates to silicon con- 7talning resinous compositions and methods of making the same includingorganic silicon derivatives containing hydrocarbon groups such asaliphatic, carbocyclic and alicyclic groups, and their conversion intoresinous materials, to the methods of making such materials, andcomposi- 'tions containing the same.

Methyl silicon oxides, ethyl silicon oxides, phenyl silicon oxides,benzyl silicon oxides and so-called methyl aryl silicones have beendescribed. These resins usually are made by the well-known reaction ofsilicon tetrachloride with an alkyl or aryl magnesium halide. However,many organo metallic compounds will react with silicon tetrahalides oralkyl orthosilicates to produce alkyl or aryl silicon halides or esters.These halides or esters are then hydrolyzed with water and the resultingalkyl or aryl silicon hydroxides are dehydrated by any suitable means toyield polymeric alkyl or aryl silicon oxides.

Among the objects of the present invention is the production of organicsilicon derivatives and resinous materials produced therefrom by new andsimple methods.

Further objects include the production of new types of such siliconderivatives and products and compositions containing the same.

Still further objects and advantages of the present invention willappear from the more detailed description set forth below, it beingunderstood that such detailed description is given by way ofillustration and explanation only, and not by way of limitation, sincevarious changes therein may be made by those skilled in the art withoutdeparting from the scope and spirit of the present invention.

This application is a continuation-in-part of an application in thenames of John B. Rust and Homer van B. Joy, Serial No. 469,542, filedDecember 19, 1942, entitled Disilicon oxide resins and process 01'making same, now abandoned,

: and is a substitute for that application.

In accordance with the present invention, it has been found that siliconoxychloride may be alkylated, arylated, aralkylated, or otherwisetreated to introduce organic groups to produce new products and to yieldresins having greater strength than prior art products. The resins thusproduced are difierent from the resinous materials here-to-fore producedin the art, they are easier to cast, and the preferred compositions cureat low temperature. Because of the properties 01' these resinousmaterials, and notably their resistance to water, it appears that thesilicon to oxychloride is the active agent, and that there is a directbond between the silicon atoms and the organic radicals.

As the silicon oxychloride there is preferably utilized the compoundSizOCls, having the boiling point 137 C. It is not necessary to utilizethe pure silicon oxychloride, but the by-product containing the samewhich is formed in the commercial production of silicon tetrachlorideand is a mixture containing such silicon oxychloride together with otherderivatives including silicon chlorides, such as disilicon hexachloridetogether with oxygenated products, may be employed. Further while theparticular silicon oxychloride Si2OC1s is preferred, other siliconoxychlorides can be utilized. Furthermore, mixtures of the siliconoxychloride together with silicon halides such as silicon tetrahalide ordisilicon hexahalide may be employed in producing copolymers.

As the hydrocarbon substituents attached to the silicon there may bepresent alkyl, aryl, olefinyl, alkenyl, alkynyl, arenyl, arynyl,aralkyl, alkaryl, alicyclic, cyclic non-aromatic, etc. groups, asillustrated for example by methyl, ethyl, propyl, butyl, amyl, hexyl,heptyl, octyl, lauryl, isoamyl, isobutyl, isopropyl, cetyl, vinyl,allyl, butenyl, the radicals from acetylene, methyl acetylene, propylacetylene, phenyl, tolyl, xenyl, xylyl, naphthyl, chlorphenyl, styryl,and radicals from such derivatives as phenyl acetylene, etc. Theseorganic radicals may be attached to the silicon itself, or to otherportions of the molecule. Mixed derivatives containing two or more ofany of the various derivatives and organic radicals referred to abovemay also be produced. The term arkyl is used herein to cover alkyl andaryl groups.

As a probable explanation of the formation of the novel resins, it isbelieved that one or more of the halogen atoms of the siliconoxychloride is replaced by organic radicals from the organo magnesiumhalides or other reactants employed. Hydrolysis of these productsprobably forms silicols. Such silicols polymerize presumably 'by loss ofwater, forming oxygen links between the various silicols. Thishypothesis satisfactorily explains the facts observed, but reference tosuch hypothesis and explanation is not intended to be limiting sinceother possibilities exist.

In producing the organic silicon derivatives in accordance with thepresent invention, various reactions may be employed, as for example, inthe reaction of the silicon oxychloride either alone or in admixture aspointed out above, with an organo magnesium halide. Any reactive 3organo metalic compoimd can be utilized which will produce the desired,reaction products such as those of zinc, lithium, etc. Reactions withGrignard type reagents such as the organo magnesium halides represent adesirable way of producing the products sought. Such reactions withGrignard type reagents may be carried out in two stages in which forexample, the organo magnesium halide is first formed and then reactedwith the silicon oxychloride or mixture containing the same, or theorgano magnesium halide or related material may be produced in situ inthe presence of the silicon oxychloride or mixture containing the same.In producing the Grignard type reagent in situ, the necessary componentssuch as magnesium, alkyl halide with or without a catalyst, are reactedin situ in the presence of the silicon compound being treated. Grignardreaction solvents such as ether may or may not be present in such insitu reactions. The Grignard type reagents produced in situ may be thmeformed from magnesium, lithium, etc. illustrating the invention as setforth below, the examples illustrate the production of the desiredderivatives by utilizing an organo magneslum halide with the siliconoxychloride but these are illustrative only and the examples are not tobe considered as limiting. The proportions in the following examples aregiven in parts by weight. Y

The products produced by the present processes are complex mixturesespecially where no solvent is used during the reaction. It is possiblethat some Si-Si linkages are formed as well as C-Si' linkages. However,again this is speculation and no limitation by way of theory isintended. However, in some cases the products-of the present inventionutilizing those reactions where the 'Grignard type reagent is preparedin situ, differs from those made by two step reactions in which theGrignard type reagent is formed separately.

The products of the invention may be hydrolysed in water and bysubsequent heating converted into hard, tough, plastic materials. On theother hand, the hydrolytic products may be dissolved in suitablesolvents and used as baking lacquer materials, for impregnation offillers, etc. Other uses will appear hereinafter.

Example 1.31.2 parts of methyl iodide were reacted in ether solutionwith 4.86 parts of magnmium. This solution was added gradually withstirring to 22.4 parts of the commercial product obtained as alay-product in the manufacture of silicon tetrachloride, boiling mainlyat 135-139 C., and containing substantial quantities of sili- I canoxychloride, this by-product being dissolved in ether. After additionhad been completed, the mixture was refluxed 1% hours, and thenhydrolyzed by pouring it on cracked ice. It was next washed repeatedlywith water to remove hydrochloric acid and magnesium salts. The etherwas removed by evaporation, and the material was heated 18 hours at40-50 C. A hard, brittle resin was formed.

Example 2.--24 parts of ethyl bromide were reacted in ether solutionwith 4.86 parts of magnesium. This solution was added gradually withstirring to 26.9 parts of the silicon oxychloride byproduct referred toin Example 1, in ether. After addition had been completed, the materialwas refluxed 2 hours. The mixture was hydrolyzed, washed, andconcentrated as previously described. After 3 days heating at 40 C. itcured to a hard, pale-yellow resin. This resin was muchstrongerthananyoftheknownmonosilicon res- 4 ins from silicontetrachloride. The resin was heated at 175 C. for 18 hours. It did notlose any of its strength and showed no change except a slight darkeningin color.

Example 3.-30.1 parts of normal butyl bromide were reacted in ethersolution with 4.86 parts of magnesium. This mixture was added graduallywith stirring to 29.9 parts of the silicon oxychloride by-product usedin Example 1, in ether. It was then hydrolyzed, washed, and concentratedas previously described. It was heated 10 days at 40 to 50 C. and thenat for 18 hours. A hard, brittle resin was formed. 18 hours heating at175 failed to cause any apparent change.

Example 4.--34.5 parts of 'phenyl bromide were reacted in ether solutionwith 4.86 parts of magnesium. This mixture was added gradually withstirring to 26.9 parts of the silicon oxychloride by-product referred toin Example 1, and then refluxed 1 hours. After hydrolyzing, washing, andconcentrating it was heated at 4050 C. for 3 days and was still liquid.It was then heated 36 hours at 100 C. which cured it to a hard, brittleresin.

Example 5.-15.1 parts of normal butyl bromide were mixed with 15.6 partsof methyl iodide and reacted in ether solution with 4.86 parts ofmagnesium. This mixture was added gradually with stirring to 26.9 partsof the silicon oxychloride by-product referred to in Example 1, andrefluxed 1% hours. It was then hydrolyzed, washed, and concentrated aspreviously described and heated 18 hours at 40-50 C., atthe end of whichtime it was fairly hard. It was heated 3 weeks longer at 40-50 C.,during which it gradually increased in strength. Nine Sward Rockerhardness readings on a dim of this material gave an average of 5'7.

Example 6.16.6 parts of normal amyl bromide were mixed with 15.6 partsof methyl iodide and reacted in ether solution with 4.86 parts ofmagnesium. This mixture was added gradually with stirring to 26.9 partsof the silicon oxychloride by-product used in Example 1, and refluxed 1%hours. After the usual hydrolysis, washing and concentration, it washeated at 40-50 C. for 18 hours. It was fairly hard at this time but didnot have much strength. Further heating at the same temperature for 3weeks greatly increased the strength.

Example 7.--15.l parts of normal butyl bromide were mixed with 16.6parts of normal amyl bromide and reacted in ether solution with 4.86parts of magnesium. This mixture was added gradually with stirring to29.9 parts of the silicon oxychloride by-product referred to in Example1, and refluxed 1 hours. It was then hydrolyzed, washed, andconcentrated as previously described. It was cured to a hard resin by 5days heating at 40-50 C.

Example 8.An ether solution of a silicon oxychloride reaction productwas prepared as described from 24.0 parts of ethyl bromide, 4.86 partsof magnesium and 24.5 parts of the silicon oxychloride by-productreferred to in Example 1. After hydrolysis and washing, 4 parts ofasbestos floats were added and after evaporation of the ether, themixture was molded for hour at C. under 320 pounds per square inchpressure.

access:

' parts of silicon tetrachloride in ether and then refluxed 1% hours.The material was hydrolyzed. washed and concentrated as previouslydescribed and was heated 4 days at 4040 C. It cured to a hard,pale-yellow resin.

Example 1.0.l2.5 parts of methyl iodide were mixed with 5.5 parts ofnormal lauryl bromide and reacted in ether solution with 2.43 parts ofmagnesium in ether solution. This solution was added graduallywithstirring to 13.5 parts of the silicon oxychloride by-productreferred to in Example 1, in ether and refluxed 2 hours. The product washydrolyzed, washed, and concentrated as previously described. It wasthen heated 18 hours at 40-50 C. and then at 120 C. for 20 hours. Arubbery resinous material was formed.

These novel silicon oxide polymers have thermal stability greater thanthe usual coating and bonding agents. They may be used as such coatingand bonding agents for example, by applying to the desired materialsafter solution in suitable solvents such as hydrocarbon solvents bothaliphatic and aromatic, such as benzene, xylene, toluene, and otheraromatic hydrocarbons, ethers such as dimethyl ether, etc., alcoholssuch as butanol, esters such as ethyl acetate, etc. In such solutionthey may be used for application as coating compositions or as bondingagents for fillers, or the polymers may be polymerized further in situin such compositions. The solutions, etc. are thus useful as protectiveand decorative coatings. added to the reaction mixture before it ispoured on ice to hydrolyze it.

While the reaction products have been particularly utilized asillustrated above in the production of hydrolyzed products followed bydehydration, other types of resinous materials may be obtained, as forexample, by. adding a moist alcohol to the reaction products beforepouring them on ice. In such instances, the alkoxy or related grouppartially replaces other substituents on the silicon. Moist ethanol maythus be employed as well as other moist alcohols individually or inadmixture, such as the aliphatic alcohols including methanol, propanol,hutanol,

phenols such as phenol, cyclic non-aromatic or alicyclic alcohols suchas cyclohexanol, and the like. Anhydrous alcohols, etc. may also be usedand the products converted into the silicon alkoxy, aryloxy, or relatedderivatives.

A variety of other utiities are available for these various reactionproducts. Thus sheet insulation may be prepared by treating woven orfelted organic or inorganic fabrics such as paper or glass, etc., withsolutions of these silicon polymers. Flaky inorganic materials such asmica may be employed in lieu of the fabrics.

The hydrolyzed or partially hydrolyzed or etherifled materials may beused as lacquers or adhesives, either alone, or in admixture with othercompletely reacted or potentially reactive resins. Similarly moldingcompositions may be prepared from such combinations. Among the resinswhich may be mentioned in this connection for inclusion are naturalresins such as rosin, copal, shellac, etc., as well as synthetic resinsincluding urea aldehyde resins, phenol aldehyde resins, melamine resins,alkyd resins, "aniline aldehyde resins, acetone formaldehyde resins,cumarone resins, polymerized vinyl derivatives and vinyl resins,polymerized acrylic derivatives including the esters of acrylic andmethacrylic acids, etc.

The solvent may be The polymers of the present invention may becompounded with cellulose derivatives, particularly cellulose esters andethers such as cellu-' lose .acetate, cellulose nitrate, ethylcellulose.

5 benzyl cellulose, etc. In some cases the hard,

brittle polymers that may be produced in accordance with the presentinvention may be powdered and used as fillers for the various 1compounding ingredients as set forth above. In

cases where these silicon resinous polymers of the present invention arecompatible with the substances with which they are to be incorporated,they may be in the form of a liquid or soft polymer of relatively lowmolecular weight.

The hard, brittle polymers produced in accordance with the presentinvention may be plasticized by the addition of suitable plastlcizingagents or by silicon or disilicon oxide resins of lower softening point.

The low molecular weight polymers may be dissolved or dispersed in oilssuch as tung oil, linseed oil, etc., alone or mixed with pigments,plasticizers and dri ers to form coating compositions or coatingcompositions of the lacquer type produced from cellulose derivatives asset forth above with these silicon polymers together with solvents maybe utilized.

Laminated products may be made by superimposing organic or inorganicfibrous sheet materlals coated and impregnated with the resins of thisinvention, and subsequently bonding the sheets together under heat andpressure The silicon derivatives either alone or in admixture with otheradditives including resins as set forth above, may be mixed with variousinorganic or organic fillers and used for hot molding, extruding,casting, etc. Objects having excellent strength and high resistance towater and organic solvents may thus be produced. The inorganic fillersinclude both fibrous and non-fibrous materials, such as the days likebentonite, mica, asbestos, glass, ce lulosic materials such as paper,cotton, wood flour, etc.

The silicon derivatives of the present invention as illustrated abovemay be used as textile finishing compositions either alone or insolution in solvents to produce special effects in or on such textiles.

The silicon derivatives prepared in accordance with the presentinvention may be used as lubricating oils or may be used as additives toboth hydrocarbon oils such as lubricating oils as well as for theinclusion with vegetable oils such as thedrying oils as illustratedabove, and also with semi-drying oils such as soya bean oil, as well asnon-drying oils including castor oil, etc. They may be blended with suchoils by cooking or other operations.

Having thus set forth our invention, we claim: 1. In the process ofmaking resinous products,

the step of replacing chlorine in silicon oxychloride with a hydrocarbongroup by reacting silicon oxychloride SizOCle with an organo magnesiumhalide reactive therewith, the organo group being alkyl of from 1 to 16carbon atoms, the proportions of oxychloride to organo magnesium halidebeing about 111.9 to 1:2.6 moles giving a reaction product containingorgano groups attached to silicon and also containing hydrolyzablechlorine attached to silicon.

2. The process of making resinous products which comprises replacingchlorine in silicon oxychloride with a hydrocarbon group by reactingsilicon oxychloride SlzOCls with an organo magnesium halide reactivetherewith, the organo grou being alkyl of from 1 to 16 carbon atoms, theproportions of oxychloride to organo magnesium halide 'being about 1:1.9to 1:2.6 moles.

3. The process as set forth in claim 1 in which the alkyl group ismethyl.

'4. The process as set forth in claim 1 in which the alkyl group isethyl. I 5. The process as set forth in claim 1 in which the alkyl groupis n-rbutyl.

6. The reaction product of silicon'oxychloride S12OClc with a Grignardreagent having the formula RMgX where R is alkyl of from 1 to 16 carbonatoms and X is halogen and the ratio of oxychloride to Grignard reagentof about 1:19 to 1:2.6 moles, the reaction product containing organogroups of the Grignard reagent attached to silicon and also containinghydrolyzable chlorine attached to silicon.

7.,A resinous product comprising the dehydrated material from thechlorine only-hydrolyzed reaction product of silicon oxychloride SizOClewith an organo magnesium halide in the ratio of about 1:1.9 to1:2.6moles, the organo group being alkyl of from 1 to 16 carbon atoms,the reaction product containing organo groups of the organo magnesiumhalide attached to silicon and also containing hydrolyzable chlorineattached to silicon.

8. A reaction product as set forth in claim 6 in which the alkyl groupis methyl.

8 9. A reaction product as set forth in claim 6 in which the alkyifgroupis ethyl.

10. A reaction product as set forth in claim 6 in which the alkyl groupis n-butyi.

JOHN B. RUST.

HOMER VAN B. JOY.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNI'I'ED STATES PATENTS Number Name I Date 2,258,218 Rochow Oct. 7,19412,253,222 Rochow Oct. '1, 1941 2,381,366 Patnode Aug. 7, 1945 FOREIGNPATENTS [Number Country Date 113,708 Australia Sept. 4, 19 41 OTHERREFERENCES Kip'ping, Proc. Royal Soc. (London) vol. A 159, 1937, pp.139-142-145.

Schumbet al., J. Amer. Chem. Soc., vol. 61, pp. 363-366 (1939), ChemicalAbstracts, vol. 33, D. '4590 (1939).

Ephraim, Inorganic Chemistry, 4th Ed., 1943, pp. 811, 832-834.

Sauer, J Chemical Education, vol. 21, June 1944, pp. 303-305.

F1i5e4ser et al., Organic Chemistry Heath 1944, p.

Emeleus et al., J'ourn. of the Chem. Soc. (London), Dec. 1947, pp.1590-1592.

1. IN THE PROCESS OF MKAING RESINOUS PRODUCTS, THE STEP OF REPLACINGCHLORINE IN SILICON OXYCHLORIDE WITH A HYDROCARBON GROUP BY REACTINGSILICON OXYCHLORIDE SI2OCL6 WITH AN ORGANO MAGNESIUM HALIDE REACTIVETHEREWITH, THE ORGANO GROUP BEING ALKYL OF FROM 1 TO 16 CARBON ATOMS,THE PROPORTIONS OF OXYCHLORIDE TO ORGANO MAGNESIUM HALIDE BEING ABOUT1:19 TO 1:26 MOLES GIVING A REACTION PRODUCT CONTAINING ORGANO GROUPSATTACHED TO SILICON AND ALSO CONTAINING HYDROLYZABLE CHLORINE ATTACHEDTO SILICON.